An improved synthesis of functionalized biphenyl-based phosphine ligands

Functionalized dicyclohexyl- and di-tert-butylphosphinobiphenyl ligands are prepared by the reaction of arylmagnesium halides with benzyne, followed by the addition of a chlorodialkylphosphine. This one-pot procedure is considerably less expensive and time-consuming than the method used previously to prepare such ligands. The cost of introducing the dicyclohexylphosphine group can be decreased by preparing chlorodicyclohexylphosphine from PCl3 and cyclohexylmagnesium chloride, and using the reagent without further purification. The new method is significant, as a variety of ligands can be produced in useful amounts by a procedure that is simple, with starting materials that are relatively inexpensive, and, in most cases, without chromatographic purification.     

Nonlinearly limited saturable-absorber mode locking of an erbium fiber laser

We describe an erbium fiber laser that is passively mode locked by a novel, precision antireflection-coated semiconductor saturable-absorber mirror that incorporates an additional two-photon absorber. It is shown that passive mode locking evolves from a Q-switching instability. The results are achieved by use of saturable absorbers that provide a large (15%) nonlinear (saturable) loss. Exploiting two-photon absorption can substantially reduce the peak power of the Q-switched pulses, which results in improved reliability of the laser. Moreover, two-photon absorption can be used to produce an optimal stability range for saturable-absorber mode locking.     

Three-dimensional Doppler velocimetry of flow jets

A closed-form solution is derived of the Doppler equation for the magnitude and angle to the three-dimensional velocity vector. The resultant solution is more general than previous formulations and, since it is based on multiple conventional transmit-receive Doppler probes, it can be readily applied by adapting existing Doppler units. Turntable experiments demonstrated that the three-dimensional angle-independent theory correctly predicted velocity within average 32% over a 26.°-range of Doppler angles. Experiments with a flow phantom showed general agreement with the angle-independent theory in the more demanding setting of an actual flow stream. Experiments utilizing a jet stream which modeled the clinically important conditions that exist in stenotic vessels, valvular abnormalities, and septal defects within 1.4-3.8% of the actual velocity, over an 18° range of Doppler angles     

Microwave Rejection Networks

This is an extension of the Bridged-T infinite rejection network idea transformed into microwave concepts. These devices achieve approximately 100db of attenuation with skirt attenuations approximately 5db. The tuning range between 1 KMc and 10 KMc is continuously covered with 4 units at present. Work is continuing to reduce the number of units to 2. Design parameters, performance curves, and application to MILSTD 826 will be discussed.     

Fluorescence in alkali-metal salts of some acyclic,resonance-stabilized carbanions

While fluorescence can be clearly observed in resonance-stabilized acyclic anions, its occurrence is insufficient for unambiguous assignment of either ion-pairing type or anion geometry. As in cyclic, aromatic anions, the requirement for contact ion-pairing is less severe in the excited state than in the ground state. The fluorescence lifetimes of acyclic anions are affected more by the associated cation than by the type of ion-pairing.     

A reactivity/affinity switch for parallel kinetic resolution: alpha-amino acid quasienantiomers and the resolution of cyclopropene carboxylic acids

A new type of parallel kinetic resolution (PKR) is reported in which quasienantiomers with very similar reactivities give products whose chromatographic properties diverge upon the addition of fluoride. This concept of a reactivity/affinity switch is applied to the PKR of cyclopropene carboxylic acids with all-carbon quaternary centers. This is the first application of alpha-amino acid quasienantiomers in PKR, and it is a complementary approach for acyltransfer systems where the asymmetry is induced by the nucleophile rather than the leaving group. Excellent diastereoselectivities (ranging from 90:10 to 99.5:5) and good yields were obtained for both quasienantiomeric products, and the reactions can be run on significant scale because the separation is trivial. High-level DFT calculations (B3LYP functional with the 6-31+G(d,p) basis set) provided transition-state structures with relative energies that are in accord with the experimental observations.     

Event shapes in deep inelastic lepton-hadron scattering

The structure of hadronic final states in deep inelastic scattering expected from QCD is analyzed in terms of the shape parameters H_l and C_l. We find that the effects of the fragmentation of quarks and gluons into hadrons are typically governed by $\text{√s = [Q}{}^2\text{(1/x?1)]}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$. For √s?30 GeV, the distributions of events in H₂ and C₂ should allow a test of the perturbative QCD prediction of three-jet events.     

Non-diffractive production of meson resonances

We study the peripheral cross sections of resonances that cannot be produced by π-exchange. In particular, we concentrate on the four meson nonets expected as L = 1 quark states (i.e., the J^P = 0⁺π_N(980); J^P = 1⁺ A₁, B; J^P = 2⁺ A₂). We use SU(3), Regge poles, factorization, exchange degeneracy, pole extrapolation, and the vector-meson-photon analogy. We predict the cross sections in both photoproduction and non-diffractive hadronic reactions. In passing, we discuss the large unnatural-parity (B, K?Q_B) exchange contributions and even the possibility of studying ππ → πω while avoiding the B production background.     

(+)-Sorangicin A synthetic studies. Construction of the C(1-15) and C(16-29) subtargets

[structure: see text] Effective stereocontrolled syntheses of subtargets (-)-2 and (-)-4, comprising respectively the C(16-29) and C(1-15) tetrahydropyran and dihydropyran moieties of the potent antibiotic (+)-sorangicin A (1), have been achieved. The cornerstone for the synthesis of (-)-2 involved an aldol tactic exploiting 1,4-induction, followed in turn by an acid-mediated cyclization/ketalization and hydrosilane reduction promoted by TMSOTf, while construction of (-)-4 entailed a stereoselective conjugate addition/alpha-oxygenation sequence.